JPS61501154A - Epoxy resin compositions and methods of making laminates therefrom - Google Patents

Abstract

An epoxy resin composition and a process for preparing electrical laminates therefrom has been disclosed. <??>The epoxy resin composition is comprised of an epoxy resin, a solvent and a hardener which is the reaction product of a hexa-alkyl ether of a methylol melamine having the general formula: <CHEM> wherein each R, independently, is an alkyl radical having from 1 to 4 carbon atoms with a polyhydric phenol and, optionally, a monohydric phenol, with the phenol compound(s) having been employed in an amount to provide a ratio of at least one reactive phenolic hyxroxy group for each alkoxy group.

Description

[Detailed description of the invention] Epoxy resin compositions and methods of making laminates therefrom The present invention provides relating to resin compositions and methods of producing electrical laminates using said compositions. do. Traditionally, laminates used in the manufacture of electrical circuit boards are The resin composition is impregnated with a resin composition, and the impregnated solution 7) is passed through a heated chamber, where the resin The resin composition is partially cured and then molded to form one or more resin mats like copper foil. It is commonly manufactured by laminating layers under heat and pressure. Ru. The resin used for impregnation is commonly called a "varnish" and the impregnated The resin cloak is commonly referred to as "prepreg." Electrical The laminate is processed into a single circuit board in a conventional manner.

Generally, epoxy resins are used to impregnate reinforced webs. For use as currently described Typical epoxy resin compositions for this purpose include bisphenol A and tetrabromine. diglycidyl ether of Mobisphenol A, dicyandiamide as a curing agent, Brominated epoxy prepared from an organic solvent such as acetone and a promoter or catalyst Consists of xyl resin. Disadvantageously, the cured varnish prepared from this varnish composition The glass transition temperature of epoxy resins is disadvantageously low, e.g. , which often causes problems in subsequent processing of the impregnated web. difference Lani.

Dicyandiamide hardener is used in varnish compositions and also in blends made therefrom. It has a tendency to crystallize on solid wood.

Another varnish composition used for reinforcing webs used in the production of electrical laminates is the diglycidyl ether of bisphenol A and bisphenol A or Consisting of a blend of trabromobisphenol A and dicyandiamide curing agent . The diglycidyl ether of bisphenol A was added in situ during the impregnation of the reinforced web. bisphenol A and/or tetrabromobisphenol A and dithia [For example, US Pat. No. 37,38,862] reference]. Disadvantageously, the varnish composition system is more expensive than the aforementioned varnish compositions. It does not exhibit a glass transition temperature, and for these and other reasons it is not widely used commercially. Not often used.

Therefore, an epoxy resin composition for the production of electrical laminates, which does not have the above-mentioned disadvantages, is available. It is highly desirable to provide a composition.

That problem is solved by the invention as defined in the claims.

Thus, in one form of embodiment, the present invention provides an epoxy resin, a curing agent, , an organic solvent and, if necessary, accelerators and other standard auxiliaries. In the xy resin composition, +4? The curing agent j has the general formula: In the formula, each R is individually 1 to Hexamethylolmelamine is an argyl group with 4 carbon atoms. one kind of sa-alkyl ether, a top piece of polyhydric phenol α, and if necessary, ]1lIfi is a reaction product with one type of phenol, and one or more of the above phenolic compound and hexa-alkyl ether of hexamethylolmelamine The ratio of hydroxyl to alkoxy groups of the reactive phenol is at least 1. The present invention provides an epoxy resin composition characterized in that the epoxy resin composition is used in an amount sufficient to Ru.

The epoxy resin composition of the present invention exhibits excellent properties, especially when cured. The resin has a substantially higher glass transition than dicyandiamide cured epoxy resins exhibiting a glass transition temperature of up to and above 160° C., and 1 The curing agent component of the resin composition of the present invention is commonly used in the production of electrical laminates. dicyandiamide is soluble in most organic solvents. The problem of curing agent crystallization is effectively eliminated. of these and other natures; Therefore, the resin composition of the present invention is compatible with varnishes used in the production of electrical laminates. Especially suitable for

In another form of embodiment, the invention therefore provides a method for manufacturing electrical laminates. Regarding how to This method includes steps: (a) epoxy resin, the epoxy resin Impregnate the reinforced web with an epoxy resin varnish consisting of a curing agent and an organic liquid. .

(b) The prepreg thus prepared is mixed with the epoxy component of the varnish as a curing agent. Heat to a temperature sufficient to partially react for minutes.

and (C) layering one or more layers of the prepreg with a conductive material, and By heating the laminate so formed to high temperatures under high pressure, The prepreg is then fabricated into an electrical laminate.

The epoxy resin varnish is the epoxy resin composition of the present invention.

Since the cured epoxy resin composition according to the present invention has a high glass transition temperature, the cured epoxy resin composition according to the present invention Reinforced electrical laminates prepared by the method of Akira do not have excessive brittleness. Figure 3 illustrates the improved thermal deformability achieved.

In addition, reinforced electrical laminates provide improved resistance to attack by various chemicals. Amazing as well, exhibiting improved resistance, low expansion coefficient and improved electrical suitability. Preferably, a single clad 1.5 mm laminate should be used during the manufacture of electrical circuit boards. Holes drilled in the board show improved properties when examined under a microscope I understand. Additionally, the drills used to drill these holes were of the same caliber. Shows reduced wear compared to drills used to drill holes in laminates However, such laminates cannot be manufactured from conventional resin compositions. It was.

In the practice of this invention, the epoxy resin component of the resin composition suitably includes more than one It is a compound having many 1,2-epoxide groups. Generally, epoxy resin components are It is a saturated or unsaturated aliphatic, cycloaliphatic, aromatic or heterocyclic compound.

It contains one or more non-interfering substituents 1, e.g. halogen atoms, phosphorus atoms, It can be substituted with hydroxyl groups and ether groups. Epoxy resin can be monomeric or polymeric.

Such epoxy resins are well known in this field and, e.g. It is described in the following literature: "Handbook of Epoxy Resins (The H. and Book, of Epoxy Re5ins) J, H, Lee and Neville, (1967): - Yaw tip tuna - Published by Hill (McGraw-H1II), Appendix 4-1.4-35 to 4-5 6 pages, and U.S. Patent No. 2,633,458; U.S. Patent No. 3,477.9 No. 90 (especially column 2.39 to column 4.75); U.S. Patent No. 3,821,243 Issues: U.S. Patent No. 3,907,719; U.S. Patent No. 3,975,397 and U.S. Pat. No. 4,071,477.

Particularly suitable epoxy resins in the practice of this invention include those of the primary 2-bis(4-hydroxyphenyl)propane (commonly called bisphenol A) ) and 2,2-bis(3,5-dibromo-4-hydroxyphenyl)pro Glycidyl ether of bread (commonly called tetrabromobisphenol A) ; Glycidyl ether of novolak resin, i.e. Formula 1: In the formula, R' is hydrogen or an alkyl group, and n is an integer of 1 to 10. Phenolaldehyde condensate: and glycidyl ether of tris(phenol) tell, i.e. For example, those described in U.S. Pat. No. 4,394,498; Alternatively, a mixture of two or more epoxy resins can also be used in the present invention. Screw Liquid glycidyl polyethers of phenol A and mixtures thereof are most preferred. Delicious.

Organic liquids suitable for use in the resin compositions of the present invention include epoxy resins and hard before and/or during and/or partial curing. is volatile enough to escape from the epoxy resin composition before final curing. Machine liquid. Examples of such organic liquids are the following two types of glycols: Ethers, such as ethylene or propylene glycol 7-methyl ether or and their esters, such as ethylene glycol monomethyl ether acetate ketones, such as methyl isobutyl ketone, methyl ethyl ketone, aceto; and methyl isopropyl ketone: and aromatic hydrocarbons such as toluene and xylene or mixtures thereof, ketones, especially acetone and methyl Sobutyl ketones or esters thereof, especially ethylene glycol monomethyl Mixtures with ether acetates are most preferred.

The amount of solvent contained in an epoxy resin composition depends on a variety of factors, such as Ingredients used, such as epoxy resins, curing agents and solvents, and epoxy resins Depending on the desired properties of the composition, e.g. viscosity and its absorption by the reinforcing web It will change.

Preferably, the epoxy resin composition is a Brookfield viscometer, model RVT, 2 50-1O as measured using 0 rpm and a suitable spindle at 25°C. It has a viscosity of OO millipascals (mPa). Generally, the amount of solvent is Will range from 20 to 80% by weight, based on the total weight of the epoxy resin composition , preferably the epoxy resin composition contains 20-60i31% solvent and 80-4 It will contain 0% by weight of non-volatile materials.

The curing agent used in the practice of this invention is a hexamethylolmelamine hexamine. It is a reaction product of lukyl ether and polyhydric phenol. In carrying out the invention Advantageously used curing agents are phenolic hydroxyls of 2 to 6 and 6 to 3 It is a polyhydric phenol compound containing 0 carbon atoms. Preferably, the present invention In the polyvalent Fe formula used in the practice, A is oxygen-sulfur: -5-s-: -co-: -5o-niSO□-1 divalent containing 11 to 10 carbon atoms Hydrocarbon group: A divalent hydrocarbon group containing oxygen, nitrogen or each X is independently hydrogen, halogen or 1-1o carbon atoms, preferably or a hydrocarbon group having 1 to 4 carbon atoms, where n is 0 or l. is the value, has. More preferably, A is a divalent hydrocarbon group having 1 to 8 carbon atoms. and each X is hydrogen. Using a mixture of two or more polyhydric phenols You can also

In the practice of the present invention, one or more polyhydric phenols and one or more or more monohydric phenols, such as p-tert-butylphenol or nonyl Mixtures with phenols can also be used in the production of hardeners. Polyvalent Fe When using a mixture of phenols and monohydric phenols, the mixture advantageously comprises 0, preferably such mixtures should contain small amounts of monohydric phenols. , from 25% by weight, based on the total weight of monohydric phenols and polyhydric phenols Contains less, more preferably less than 15% by weight of monohydric phenols.

Most preferably, in the practice of the invention, the phenol is a dihydric phenol, especially a dihydric phenol. 2,2-bis(4-hydroxyphenyl)propane, usually bisphenol A (BBA) is a phenol.

Hexa-alkyl ester of hexamethylolmelamine used in the practice of this invention is often referred to as an aminotriazine, in which each R independently represents It is an alkyl group having 1 to 4 carbon atoms. Hexamethiol like this Examples of hexa-alkyl ethers of melamine are as follows. Hexameth oxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethyl Melamine, hexaisopropoxymethylmelamine, hexa-1-butoxymethyl Melamine, and hexaisobutoxymethylmelamine, hexamethylolmelamine One or a mixture of two or more hexa-alkyl ethers are used here. You can also do that. Hexamethoxymethylmelamine is most preferred.

The curing agent has a ratio of phenol hydroxyl epi-alkoxy groups of at least 1, preferably phenol and hexamethyloyl, preferably using amounts of reactants ranging from 11 to 28 prepared by reacting hexa-alkyl ether of melamine with Ru. The ratio of hydroxyl epi-alkoxy groups of phenol is determined by the epoxy resin composition and and the properties of the laminate made from it. For example, The laminate has a lower ratio of hydroxyl-epi-alkoxy groups than Fairnow 1. Excellent heat resistance, e.g. high glass transition when made from poxy resin compositions temperature, and other improved properties. In general, the phenolic fraction of less than 2 Using the ratio of droxyl epi-alkoxy groups is generally desirable for superior #thermal Preferably, the hydroxyl depletion of the phenol will be suitable to achieve the The ratio of alkoxy groups is between 1.2:1 and 1.95:1, most preferably 1.4:1. The ratio is 1 to 1.9:1.

In the preparation of hardeners, the hexaalcohol of phenol and hexamethylolmelamine The reaction with the kill ether converts the curing agent into a highly phenolic hydroxyl epi-alcoholic compound. In the ratio of hydroxyl groups, i.e., from 2.2 to 2.2, When prepared in the ratio of xyl groups, it can be carried out in the presence of volatile organic diluents. can. In such cases, a catalyst is usually not required in the reaction mixture. one Generally, suitable reactions are carried out at temperatures between 120 and 200°C, and completion of the reaction is This is indicated by the cessation of generation of m alcohols corresponding to the alkoxy groups.

The curing agent preferably has a low phenolic hydroxyl to epi-alkoxy ratio, i.e. i.e., at a ratio of hydroxyl groups to alkoxy groups of the phenol of 1 to 2, the diluent and under reaction conditions as described in U.S. Pat. No. 4,393,181. When preparing the gelled material before the desired conversion of hexamethylolmelamine is produced, which is not soluble in organic solvents.

In order to obtain reaction products that are satisfactorily soluble in organic solvents, it is necessary to Hexamethylolmelamine and phenol in the presence of a catalyst using a diluent A preferred method is used which consists of reacting with a xa-alkyl ether. theory The disclosed method advantageously reduces the hydroxyl drop of the desired phenol in the preparation of the curing agent. The ratio of alkoxy groups used in the curing agent formulation is the preferred low It is particularly useful in the ratio of hydroxyl to alkoxy groups of phenols.

This reaction is advantageously carried out at elevated temperatures, preferably from 80 to 250°C, more preferably from 100 to 250°C. It is carried out at a temperature of 200°C.

In general, phenolic compounds and hexa-alkyl ethers of hexamethylolmelamine The reaction with ester is indicated by the cessation of the generation of m alcohols corresponding to the alkoxy group. the corresponding epoxy resin composition prepared from it. It is desirable to achieve the highest glass transition temperature of the cured resin; Unresponsive alkoxy groups may react under the curing conditions of the epoxy resin, This produces a liquid (i.e., -hydric alcohol) by releasing the -hydric alcohol. It seems that this will give rise to the basis of Therefore, the unreacted alkoxy group The main amount is that liquid seedlings create processing problems in the manufacture of laminates. sell.

The organic liquid diluents preferably used in this reaction are phenol and hexane. Organic compounds in which the starting materials of samemethylolmelamine and their reaction products are soluble It is a liquid. Preferably, the organic liquid diluent is inert to the reaction and Formed during the reaction of nol and hexamethylolmelamine with alkyl ethers It boils at a temperature higher than the boiling point of m alcohols. Additionally, organic volatile reactions The diluent is advantageously the epoxy to be prepared using the reaction product as a hardener. Suitable as a zero-reactive diluent, which can be used as a solvent for resin compositions Examples of organic liquids used are generally as solvents for the epoxy resin component of the composition. It is a useful organic liquid. Esters, especially ethylene glycol 7-methyl ester -teracetate and ketones, especially lower ketones, e.g. methyl isobutyl Ketones are preferred.

The organic liquid reaction diluent is prepared by using both a volatile diluent and a non-volatile diluent. Used in an amount of 5 to 80% by weight, based on the total weight of one reaction mixture involved. Ru. Preferably, the reaction mixture contains 10-60% by weight organic liquid reaction diluent. There will be.

For the reaction of phenol and hexamethylolmelamine with hexa-alkyl ether The catalysts used in Bronsted) acids. Such acids include, for example, monocarboxylic acids or are dicarboxylic acids such as para-toluenesulfonic acid and mineral acids such as sulfuric acid. or hydrochloric acid. The acid catalyst is used in an amount sufficient to catalyze the reaction.

Such amounts will depend on various factors, such as the particular starting materials and the particular catalyst used. Although this can vary depending on the medium and the specific reaction conditions, the catalyst is generally a phenol. based on the total weight of the hexa-alkyl ether of hexamethylol and hexamethylolmelamine. Then, 0.01 to 0.2. Preferably used in an amount of 0.05 to 0.5% by weight. Ru.

The reaction between the hexa-alkyl ether of hexamethylolmelamine and phenol is When complete, the reaction product is subsequently removed from the organic liquid diluent by evaporation of the diluent. It can be recovered. Organic form diluents generally include the epoxy resin compositions of the present invention. It is used as a solvent or a component of a solvent, and its separation is generally unnecessary.

The amount of curing agent used in the epoxy resin varnish compositions of the present invention depends on various factors: For example, the particular curing agent and particular resin used, and the nature of the composition and its Depends on end use. Generally, the proportion of curing agent in an epoxy resin composition is the highest selected to provide a cured epoxy resin composition exhibiting a glass transition temperature of Ru. Generally, such amount is the hydroxyl of the phenolic in the hardening agent The ratio of epoxy groups in the epoxy resin component in the composition is from 0.5:1 to 2:1. Preferably, the curing agent will convert the epoxy resin composition into epoxy groups. used in an amount such that it contains 0.8 to 1.2 phenolic hydroxyl groups per Ru.

The epoxy resin composition of the present invention may have a bond between the curing agent and the epoxy resin, if necessary. It may contain promoters for the reaction. Various substances that catalyze this reaction Typical examples are stannous salts of monocarboxylic acids such as stannous octoate and stannous salts of monocarboxylic acids. and stannous heterocyclic compounds, such as imidazole and benzimidazole. compounds and their salts, tertiary amine porates and tertiary amines. here Useful heterocyclic compounds generally contain substituted C═N-C groups or and a secondary amino group, that is, a =NH group. These complex Cyclic compounds include imidazoles, substituted imidazoles and substituted bases of the formula Including zuimidazoles: where R'' is independently hydrogen, halogen or an organic group, such as a hydrocarbon group or is a substituted hydrocarbon group. Examples of substituted hydrocarbon groups are ester, ether, amide , imide, amine, halogen and mercapto-substituted hydrocarbon groups. good Preferably, each R'' is hydrogen or a hydrocarbon group having 1 to 4 carbon atoms.

Preferred accelerators are imidazoles such as 2-methylimidazole and tertiary An amine, for example benzyldimethylamine. Most preferably, the accelerator is dimethylamine or 2-methylimidazole.

The promoter is generally used in an amount sufficient to catalyze the reaction. such an amount depends on the specific starting materials used, e.g. accelerators, epoxy resins and hardeners. The accelerator is generally the sum of the epoxy resin and hardener, although It is used in amounts of 0.01 to 5% by weight, based on weight. Preferably, the accelerator is , in an amount of 0.02-3% by weight, based on the total weight of epoxy resin and curing agent. used.

The varnish composition of the present invention preferably comprises 5 to 50% by weight, most preferably 15 to 50% by weight. 40% by weight epoxy resin; 5-40% by weight, preferably 115-35% by weight Curing agent: consisting of 25-55% by weight of organic solvent and 0.02-2% by weight of accelerator. The weight percentages are based on the total weight of the composition.

In the practice of this invention, other substances may also be added to the epoxy resin compositions of this invention. or mixed. Such substances are usually supplemented with adjuvants, for example pigments or Pigments, thixotropic agents, flow regulators and stabilizers.

The epoxy resin compositions of the invention can be used, for example, in particular for preparing electrical laminates. Various different materials such as glass, quartz, carbon, aramid and boron fibers is particularly useful for impregnating textiles, webs, foils and cloths from . In the manufacture of electrical laminates, glass fibers and the epoxy of the present invention are generally used. A resin composition is used.

In the method of the present invention for producing electrical laminates, an epoxy resin reinforced web is in the desired amount and subsequently heat this web to pre-cure the epoxy resin. The amount of epoxy resin applied to the reinforcing web depends on the particular reinforcing web and the particular Epoxy resin composition, desired properties of the impregnated material and electrical fabricated therefrom Although this may vary depending on the target laminate, the epoxy resin composition of the present invention generally has a , combined with the reinforcing web in the ratio of ordinary amounts, based on the total weight of the impregnated web. In this case, an epoxy resin composition of 30 to 70% by weight is used.

The impregnated web or prepreg is subsequently processed by conventional techniques. this Such technology involves heating the impregnated web to high temperatures such as 100-200°C. and subsequent curing, including pre-curing and partially curing the epoxy resin, respectively. Then, the prepreg is laminated. Here, one or several sheets of prepreg are laminated. Bond and subsequently cut to predetermined size and thin layer of conductive material , for example, when combined with wA foil under high temperature and pressure. The bed temperature varies between 130 and 230℃, and the pressure varies between 34kPa and 6.9MP It varies between a.

In the following examples, epoxy resins are designated as: r-r-ho+shim Fat A” Ha, 160-1900) x-:t! 4-n” 4F4 (E EW) 8. Epoxidized phenol/formaldehyde novola with a functionality of 5.6 It is a resin.

"Epoxy resin B" is a tetrabromohyphenate having an EEW of 430 to 470. It is diglycidyl ether of Nor-A.

"Epoxy resin C" has an EEWJ of 177-188 and 7-10 at 25°C. It is a diglycidyl ether of bisphenol A with a viscosity of Pa.

"Epoxy resin D" is tetrabromobisphenol A with an EE of 400 to 475. Jig of Bisphenol A with EEW of 182-192 with molecular weight increased to W It is lysidyl ether. Epoxy resin is 80% epoxy resin in acetone. Use as a % solution.

In the following examples, all parts and percentages are by weight unless otherwise specified. evening.

Jacketed stainless steel equipped with a stirrer, means of condensation and heating, and a cooler In a steel reactor, add 25 parts of hexamethoxymethylmelamminerosymel (Cym el [phase]) 303, available from American Fist Cyanamide], 25 parts. Ethylene glycol monomethyl ether acetate and 75 parts of bisphenol Le A was supplied. This reaction mixture converted 1.71 phenol OH groups to each alkyl Contains per xyl group. Heat this mixture to 80°C under a blanket of nitrogen. did. When this mixture was obtained at this temperature, 0.09 part of oxalic acid dihydrogen was added as a catalyst. The temperature of the resulting mixture was increased to 110-115°C. At this time, measurable amounts of methanol began to distill out. Here the reaction mixture The mixture was slowly heated to 142-145°C for an additional 2 hours, and the methanol continued to distill off. The reactor mass was maintained at this temperature for an additional hour. at the end of this time When methanol is no longer generated from the reaction mixture, cool the reactor to room temperature. Cool and then dilute with 65.5 parts of methyl isobutyl ketone to give 50% solids by weight. A solution containing the components was formed.

Based on the solids content of the resulting solution, the hydroxyl content of phenol is 8.1 wt. % of phenol, i.e., 0.48 hydroxides of phenol per loog of solid material. It was Roxyl equivalent.

B. Epoxy fat varnish set. 41.5 parts of the previously prepared hardener (i.e., 83 parts of 50% hardener solution) 21.9 parts of epoxy resin 0.36.7 parts of epoxy resin B, 14.7 parts of Tor By mixing with Ene and 0.094 parts of 2-methyl imidatool, A resin solution was prepared. The solids content of this composition was 63%. This varnish set The product has a Brookfield viscosity of 3808 at 150°C and O, 15Pa. Plate gel time of 171 seconds at +8 and 170°C me). The plate gelation time is the rubber gelled by the epoxy resin in the varnish composition. It is a measure of the speed at which a substance hardens into a mass. It is possible for temperature control equipment to withstand temperature fluctuations of ±1°C. This was determined using a thermoelectric hardening plate with a After the plate has stabilized at the desired temperature, The three compositions, each containing 0.3 to 0.4 ml of the varnish composition placed in the center of the board, are in contact with the board. When I touched it, I started the stopwatch. Spread the molten resin with a spatula. and moved it from one side of the board to the other. Every 5 seconds, apply the spatula to the varnish composition. It rapidly pulled away from the object, pulling the polymer string with it. string Record the gelation time as the time when can no longer be drawn from the polymer mass. Ta.

C, to laminate The resulting varnish composition was used to coat glass cloth [Margls 7]. 628 Finish 782]. This cloth has been treated with finishing agent 782. Equal weft and warp industrial glass silk cloth (plain weave) of air grade glass. This glass silk cloth is then impregnated with the varnish in a vertical treatment device, where Zero-order in which 320g (±log) of the resin composition was applied to 1m2 of cloth. Then, the impregnated cloth is treated at a temperature of 125-150°C to release the epoxy resin. Accelerated hardening.

This pre-cured prepreg is then coated with 1-ply copper foil and 9-ply pre-cured prepreg. Fabricated in "FR-4" type electrical laminate containing preg. This laminate The laminate was heated to 130℃ for 20 minutes and maintained at a temperature of 130℃ for 60 minutes. Heat to 170-180℃ for 15 minutes and laminate at this temperature for 120-180 minutes. Cool for 20 minutes with water or 50 minutes with air and water. The epoxy resin of this laminate was cured by. pressure during this curing stage Power is 50kg/am2-r, Netstal 300 door ( 7) Added at P L/4.

Glass transition temperature and Z-axis shape of cured epoxy resin prepared from varnish composition Copper Peat Strength th) was measured on the resulting laminate. Additionally, pressure shoe the laminate. All this information was put through the pressure cooker test. The results of such tests are listed in Table 1.

-X application 21.8 parts epoxy resin A, 36.7 parts epoxy resin B, 41.5 parts cured Agent A (i.e., 83 parts of a 50% solution of Curing Agent A), 0.032 parts of 2-methyl Epoxy by mixing limidazole and 21.3 parts toluene A resin varnish composition was prepared. The solids content of the resulting composition was 61.3%.

This varnish composition was tested on a Brookfield viscometer, type RVT, at 25°C. 0.19 Pa measured using 50 rpm and a suitable spindle. It had a Kuffield viscosity. The curing time of the varnish composition determined by plate gelation is 1 It was 189 seconds at 70°C. The glass transition temperature of cured epoxy resin Measure and record on the surface work.

A laminate was prepared using the same technique used in Example 1. La Measure the physical properties of the laminate and record on the surface.

- Comparison of Nu-Iku- According to the prior art, 125 parts by weight of epoxy resin D, 3 parts by weight of dicyandiamide and 0.42 parts by weight of N,N'-dimethylbenzylamine and an appropriate amount of solvent. A varnish composition was prepared by mixing. Eating prepared from this composition Measure the glass transition temperature of the poxy resin and record it on the surface.

The laminate was prepared with a similar method to that used in Examples 1 and 2. did. The physical properties of these laminates were measured and recorded in Table I.

Table I Example 1 Example 2 Comparative test A Glass transition temperature (Tg) 150-15 170-17 118℃ 5 5 Z@expansion coefficient (1) XIO-' Front Tg 7 5 8 Rear Tg 21 23 30 Pressure Kunker test, 2 3 1 time (2) Dielectric loss factor (3) 75℃　0.0020　0.0024　0.0080100″c　O,0027 0,00310,0102125°CO,00450,00380,05151 50℃ 0.0178 0.0121 0.0790 Copper pearl strength 4) 3. 2’3.5 3.7kPa/2.5cm (1) The Z-axis leg tension coefficient is determined by thermomechanical analysis as the temperature increases. It is a measure of the expansion of the sample thickness.

(2) The pressure Kutzker test is performed by testing the sample at 2 bar and 121°C above the boiling point of water. Cooking in an atmosphere of Dip into the solder bath for 20 seconds and inspect the sample for blisters. It is a measure of the temperature resistance of a sample, determined accordingly. The time shown is to swell the sample. The number of hours that can be spent during subsequent immersion in a solder bath without Was.

(3) The dielectric loss factor is the Schering Bridge. , 500 volts, 50 Hz, using a ring electrode with an area of 20 parts cm2. Measure and indicate the electrical insulation properties of the laminate.

(4) Copper pearl strength was determined to be 2 by Instrom tester. ．． Measurements were made using a 54 cm (1 inch wide) sample. it is copper laminate [Yates copper foil (1 oz.), treated TW].

As can be seen from Table I, the cured resin composition prepared from the epoxy resin composition of the present invention The glass transition temperature of epoxy resins prepared from prior art varnish compositions is substantially higher than that of the cured resin. Furthermore, the Z-axis leg tension coefficient is the same as the dielectric loss factor. As desired for laminates prepared from the varnish compositions of the present invention, stomach.

Three electrical laminates between the phenolic paper top board and the wood bottom board. The porosity of the laminate was determined by pinching. This sandwich, 0 ．． Sphinx typical for such holes with a diameter of 95 mm ) Holes were drilled with a quality drill. Operate the drill at a speed of 48.50 rpm. t, 2400 (7) holes (8ooo holes/laminate board) at 140 holes/min I drilled the hole at speed. A micrograph is taken of the hole in the hard hole, and the drill is Inspected for wear.

The drill used for the holes in the sandwich made from the laminate of Example 1 was: Very low when compared to the drill used to drill holes in the laminate in comparative test A. Showed wear. used for sandwiches made from the laminate of Example 2. The drill wear was between that of Example 1 and Comparative Test A.

15 parts hexamethoxymethylmelamine, 45 parts bisphenol A and 15 parts parts of ethylene glycol monomethyl ether acetate are mixed at room temperature, The resulting mixture was then heated to 90°C under a nitrogen blanket. Thus, a hardening agent solution (hardening agent B) was prepared. To this resulting mixture was added 0.09 part of Oxalic dianhydride is added and the resulting reaction mixture is subsequently heated to 140°C for 3 Heat for an hour. The reaction mixture was maintained at 140°C for an additional hour and the At time 0, the evolution of methanol from the reaction mixture has ceased, and then the reaction mixture The material was diluted with 28.7 parts of methyl isobutyl ketone to give 55.26% solids by weight. A solution containing 0.0 min was then formed and the curing agent solution was cooled to room temperature. can get The kinematic viscosity of the solution at 25°C is 2190 centistokes (0,00219 m 2/s). Based on the total solids content of the resulting solution, The content of droxyl is 7.73% by weight, i.e. per 100 g of solid material. The hydroxyl equivalent was 0.45 phenol.

B. Manufacture of epoxy resin disease 28 parts of epoxy resin A, 47 parts of epoxy resin B and 25 parts of methyl isobutylene An epoxy resin solution was prepared by mixing tilketone. This solution is Kinematic viscosity of 550 centistokes, based on the total weight of solids in the solution 14 It had an EEW of 198 based on an epoxy content of 43 and solids content.

C, epoxy wood group'' 132 parts of the above epoxy resin solution, 133 parts of hardening agent B solution, 1 part of methanol 2-, 5% solution of methylimidazole and 48.9 parts of methylisobutyl An epoxy resin composition was prepared by mixing ketones.

This varnish composition contains 5532% solids and at 150°C It exhibited a plate gelation time of 195 seconds at 50 seconds and 175°C. This hardened The resin exhibits a glass transition temperature of 170-175°C, as determined by suggestive thermal analysis. Ta.

=1 treatment 4-7 Following the general procedure of Example 1, the diluent, phenol and One series of curing using specific conditions regarding the concentration of hexamethylolmelamine The agents (curing agents C, D, E and F) were prepared.

−Ikuichi Curing agent type C (5) D E F starting material (parts) HMMM (1) 25 27 30 35 Bisphenol A75 73 60 65 alkoxy OH1,711,541,281,,06 solvent, parts ethylene glycol Lumonoethyl 21 25 25 25 33.6 Teracetate Reaction conditions (2) Time, time 4.5 5.0 5.5 2 Final reaction temperature, 150 145 150　120℃ Yield, % (3) 92 92 80 63 Phenol OH 18,197,916 ,926,28%(4) (1) HMMM = hexamethoxymethylmelamine (2) The reaction conditions are the total reaction The reaction time includes the time at which the reaction is mixed and the final room temperature, and the total reaction time is Heating the mixture, including the initial generation time of methanol, the final room temperature, mixing This is the highest temperature at which something can be heated.

(3) Yield is the amount of reacted HMMM determined by the amount of methanol distillate. % of lucoxy groups.

(4) Phenol OH was expressed as weight percent of solids in the final product. Fe is the hydroxyl content of nol.

(5) When reacted according to the method of U.S. Patent No. 4,393,181, 75 parts of bisphenol A and 25 parts of HMMM dissolved in an organic liquid. It was found that no irreversible gel was formed. Therefore, this product corresponds to It could not be used for the preparation of epoxy resin compositions. US Patent No. 4゜3 When using the technique of No. 93.181, the hydroxyl drop of the phenol in the reaction mixture Non-gelling products are obtained only when the ratio of alkoxy groups is greater than 2.2. be able to.

Epoxy resin compositions (sample Nos. 4 to 7) were added to the curing agent solution, epoxy resin B and Prepared from each of C and 2-methylimidazole at the concentrations specified in Table ■ did. The amount of acetone was selected for each of the 0 compositions to form a 60% solution. The gelation time and glass transition temperature were determined; the corresponding results are listed in the front page. .

-Hinunu 1- The reaction product of hexamethoxymethylmelamine/bisphenol A was 4.393,181, 16 parts HMMM and 84 parts Bisphene. This was prepared by blending Nord A (without solvent and catalyst). The mixture contained 3g4 phenolic hydroxy groups for each methoxy group. . The mixture was slowly heated to 165°C over a period of 2 hours, and this temperature The mixture was maintained for an additional 2 hours until methanol evolution substantially ceased. Yield is 94% It was found that the product (curing agent G) was a pale brittle substance when cooled to room temperature. It was solid. The product contains 9.84% phenol based on the total weight of curing agent. This curing agent was then used to form an epoxy resin and a 2-methyl Epoxy resin compositions were prepared using limidazole in the amounts specified in Table ■ . Use acetone as an additional solvent in an amount sufficient to prepare a 60% by weight solution did.

-human village- Direct price N Uni A has a glossy body and Epoxy resin set Compound (1) prescription, department Curing agent C39,5--- Curing agent D-40,2--- Curing agent E --43,0-- Curing agent F ---44,5- Curing agent G---36,5 Epoxy resin B 37.5 37.5 37.5 37.5 37.5 epoxy Resin C2322, 319, 51826 gelling time 175℃, seconds 128 103 121 149 210 Crow transition temperature degree, “C(3) 153 157 149 153 135 (1) Resin compound is an epoxy resin versus hardness that gives equal amounts of phenolic OH groups and epoxy groups. It was prepared by adjusting the ratio of curing agent. Instructions for parts of each ingredient are based on the solids content of the 6 compositions. The curing agent is used in an amount such that it contains an amount of phenolic OH groups and epoxy groups.

(2) Gel time is a measure of the reactivity of an epoxy resin. It is described in Example 1. This was determined using the method described below.

(3) The glass transition temperature of the cured film of the epoxy resin composition is determined by the suggested heat content. It was measured using analysis.

As is clear from Examples 4 to 7 and Comparative Test B and the data recorded in Table ■ , the reactivity and curing of epoxy resins prepared from the epoxy resin compositions of the present invention. The properties of the epoxy resin are that the phenol OH group versus the alkoxy group in the preparation of the curing agent Depends on the ratio of groups. In particular, the preferred low ratio of phenolic OH groups to alkoxy groups (i.e. ratio of phenolic OH groups to alkoxy groups lower than 1 to 2) The glass transition temperature of the cured epoxy resin Compared to that of an epoxy resin cured using a curing agent prepared in the ratio of significantly higher.

Issho Shimawari 1- 48 parts of 50% hardener B solution, 45 parts of epoxy resin C, 131 parts of tetrabromo Bisphenol A, 9.4 parts ethylene glycol methyl ether and 0 ．． A varnish composition was prepared by mixing 1 part of 2-methylimidazole. Ta.

The resulting varnish composition has a solids content of 75% and is manufactured by Brookfield. The hard viscosity is 180 Pa at 25°C, and the plate gelation time is 170°C. It took 210 seconds. The cured epoxy resin has a glass transition temperature of 135°C. Indicated.

A glass cloth was manually impregnated with this epoxy resin composition and heated to 180°C in a furnace. A prepreg was prepared by drying for 120 seconds. 8 plies together Press and laminate at a maximum pressure of 40 kg/cm2 and a maximum temperature of 180°C. formed a nate. The temperature and pressure were maintained for 1 hour.

Ichido comparison test day- 31 parts of tetrabromobisphenol A, 69 parts of epoxy resin C13, 5 parts of dicyandiamide, 0.2 part N,N'-dimethylbenzylamine (as accelerator) ) and a sufficient amount of ethylene glycol methyl ether. A varnish composition was prepared. This 60% composition was cured and cured. The epoxy resin exhibited a glass transition temperature of only 118°C. Also, this comparison test A laminate was made using the method of Example 8 from the experimental varnish composition. Zishian Due to the poor thermal properties of epoxy resins cured using diamide, these resins are The laminate is a highly heat deformable water produced in Example 8. I didn't.

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Claims (1)

[Claims] 1. Epoxy resin, curing agent, organic solvent and, if necessary, accelerator and other In epoxy resin compositions consisting of standard adjuvants, the curing agent is one-stage: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ in which each R is an alkyl group having 1 to 4 carbon atoms; Hexaalkyl ether of tyrolmelamine, polyhydric phenol and necessary is a reaction product with one type of monovalent phenol, and the phenol compound The ratio of hydroxyl groups to alkoxy groups of the reactive phenol is at least 1. An epoxy resin composition characterized in that it is used in an amount sufficient to. 2. Eboxy resin is 2,2-bis(4-hydroxyphenyl)propane, 2.2 -bis(3,5-dibromo4-hydroxyphenyl)propanes or their Mixture glycidyl polyether, novolac resin glycidyl ether or Claims characterized in that it is glycidyl ether of tris (phenol) 1. The epoxy resin composition according to 1. 3. Phenol and hexamethylol melamine alcohol used in the preparation of hardeners Kill ethers increase the hydroxyl to alkoxy ratio of reactive phenols by more than 2. Claim 1 or 2, characterized in that the amount of Eboxy resin composition. 4. In the preparation of curing agents, the ratio of phenol hydroxyl groups to alkoxy groups is 1.2 to 1.95, and the hydroxyl group of the curing agent phenol to Claim 3, characterized in that the ratio of epoxy groups in the oxy resin is 0.5 to 2. The epoxy resin composition described. 5. The phenol used to prepare the curing agent has a general structural formula: ▲Mathematical formula, chemical formula, table, etc. There is▼ In the formula, A is oxygen; sulfur; -S-S-; -CO-; -SO2-; 1 to 10 carbons Divalent hydrocarbon group containing elementary atoms; divalent containing oxygen, sulfur or nitrogen is a hydrocarbon group or a covalent bond, and each X is independently hydrogen, halogen, or 1 to 1 A hydrocarbon group having 0 carbon atoms, preferably 1 to 4 carbon atoms; and n has a value of 0 or 1, Claim 1 characterized in that it is a dihydric phenol or a mixture thereof. , 2, 3 or 4. 6. A is a divalent hydrocarbon group having 1 to 8 carbon atoms, and each X is water 6. The epoxy resin composition according to claim 5, wherein the epoxy resin composition is 7. Polyhydric phenol must be 2,2-(4-hydroxyphenyl)propane The epoxy resin composition according to claim 6, characterized in that: 8. Hexaalkyl ether of hexamethylolmelamine is hexamethoxymethane. Chilmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine hexaisopropoxymethylmelamine, hexa-1-butoxymethylmelamine melamine, hexisobutoxymethylmelamine or a mixture thereof. The epoxy resin composition according to claim 5. 9. Polyhydric phenol is 2,2-bis(4-hydroxyphenyl)propane. , and the hexaalkyl ether of hexamethylolmelamine is hexamethoxy The epoxy resin composition according to claim 8, characterized in that it is dimethylmelamine. A product. 10. The solvent is ester, glycol ether, ketone, aromatic hydrocarbon or the like. and the composition contains 20 to 80% by weight of solvent. The epoxy resin composition according to claim 4, characterized in that: 11. The solvent is ethylene glycol monoethyl ether acetate, ketone or The epoxy resin composition according to claim 4, which is a mixture thereof. thing. 12. The composition may contain from 0.01 to 5 weights as an accelerator, based on the weight of the curing agent. % of stannous salts, alkali metal salts, and imidazoles of monocarboxylic acids. or benzimidazole compounds or their salts, tertiary amine borates or The epoxy resin composition according to claim 4, characterized in that it contains a tertiary amine. thing. 13. The accelerator is an alkyl-substituted imidazole or a tertiary amine. The epoxy resin composition according to claim 12. 14. The composition further comprises tetrabromobisphenol A. The epoxy resin composition according to claim 1. 15. Process: (a) an epoxy resin containing an epoxy resin, a curing agent for the epoxy resin, and an organic liquid; (b) impregnating the reinforced web with a xylene varnish composition; The rev reg should be heated sufficiently to allow the epoxy component of the varnish to partially react with the hardener component. (c) coating one or more layers of said bleb leg with a conductive material; laminated and exposed the laminate of bleb regs so prepared to high pressure. The bleb legs are made into an electrical laminate by heating to a high temperature. , In the method of manufacturing an electrical laminate consisting of The base is the epoxy resin composition according to any one of claims 1 to 14. How to make it a sign. 16. Step (b) of partial reaction between the epoxy resin and the curing agent at 100-200°C. and the lamination step (c) is carried out at a temperature of 130-230 °C and 3 Claim 1 characterized in that the process is carried out at a pressure of 4 KPa to 6.9 MPa. The method described in 5. 17. An electrical device manufactured by the method according to claim 15. laminate. 18, characterized in that it is manufactured from the electrical laminate according to claim 17. printed circuit board.